Use of 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives as biocidal agents in aqueous systems and cooling lubricants comprising these

ABSTRACT

1,3,5-Triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives of the general formula (I): 1,3,5-triazine-2,4,6-tris NH--(CH 2 ) n  --CO--O--R 1  ! are employed as biocidal or biostatic agents in aqueous systems, in particular in cooling lubricants. Fungicides, for example pyrithione or derivatives thereof and/or N-alkyl-diazenium dioxide salts, can be added to the aqueous systems. 0.05 to 0.40% by weight of the 1,3,5-triazine-2,4,6-alkylaminocarboxylic acid derivatives and 0.0001 to 0.2% by weight of fungicides are sufficient to maintain the biocidal or biostatic actions.

This application is a 371 of PCT/EP92/02248 filed Sep. 29, 1992.

The invention relates to 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylicacid derivatives, their use as biocidal or biostatic agents in aqueoussystems and cooling lubricants comprising these. Thetriazinetricarboxylic acids on which the derivatives are based, that isto say the 2,4,6-tris(omega'-carboxyalkylamino)-1,3,5-triazines, called1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids below, aredescribed in J. Prakt. Chemie, 23 (1963), pages 173 to 185 and in EP-B 0046 139. EP-B 0 046 139 furthermore relates to the use of thetriazinetricarboxylic acids mentioned and alkali metal and mono-, di- ortriethanolammonium salts thereof as corrosion inhibitors in aqueoussystems.

An anticorrosion agent which comprises an imidazoline, one of thetriazinetricarboxylic acids mentioned and at least one mono-, di- ortrialkanolamine and water is described in EP-A 0 262 086. The corrosioninhibitors according to EP-B 0 046 139 and EP-A 0 262 086 are added toaqueous systems, for example cooling liquids, cooling lubricants, paintsor cleaners, which in turn contain further additives, for examplebiocides. Additives which have been used to date are halogen-containingcompounds and, for example, boric acid and reaction products of boricacid with alkanolamines, see Ullmanns Encyklopadie der technischenChemie (Ullmann's Encyclopedia of Industrial Chemistry), 4th Edition,Volume 8, Verlag Chemie, Weinheim 1974, pages 653-655. In other cases,formaldehyde or formaldehyde derivatives have been added as biocide.However, halogen-containing compounds, boric acid and boric acidderivatives and also formaldehyde and derivatives thereof areundesirable for various reasons. There is therefore an increasing needfor biocidal agents which can be used in aqueous systems and are freefrom halogen-containing compounds, formaldehyde, formaldehydederivatives, boric acid or boric acid derivatives.

It has now been found that the1,3,5-triazine-tris-2,4,6-alkylaminocarboxylic acid derivatives of thegeneral formula ##STR1## in which

n denotes a number in the range from 4 to 11 and

R¹ has one of the following meanings:

a) an alkali metal atom, one molar equivalent of an alkaline earth metalatom or an ammonium ion derived from an alkanolamine of the generalformula

    (R.sup.2).sub.3 N                                          (II)

in which

at least one of the groups R² denotes

aa) a hydroxyalkyl group having 2 to 4 carbon atoms,

bb) a hydroxyalkyl-oxyalkylene group having in each case 2 to 4 carbonatoms in the hydroxyalkyl and oxyalkyl radical or

cc) a dihydroxyalkyl group having 3 to 6 carbon atoms

and, if less than three of the groups R² have the above meaning, theother groups R² are hydrogen, or one of the groups R² has theabovementioned meanings, the second is an alkyl group having 1 to 6carbon atoms and the third is hydrogen,

b) a straight-chain or branched alkyl or alkenyl group having 1 to 23carbon atoms,

c) a cycloalkyl group having 5 to 6 carbon atoms in the cyclic radical,which is optionally substituted by an alkyl group having 1 to 4 carbonatoms or by several groups,

d) a radical of a polyol having 2 to 15 carbon atoms and 2 to 6 hydroxylgroups, including addition products of ethylene oxide and/or propyleneoxide onto the abovementioned polyols,

e) a radical of an addition product of ethylene oxide and/or propyleneoxide on straight-chain or branched alcohols having 6 to 22 carbonatoms,

f) a radical of a polyethylene, polypropylene or mixedpolyethylene/polypropylene glycol, the free hydroxyl group of which isoptionally substituted by an alkyl group having 1 to 4 carbon atoms,

g) a radical of a hydroxycarboxylic acid having 2 to 18 carbon atoms,

h) a phenylalkyl group having 1 to 4 carbon atoms in the alkyl radical

or

i) a radical of an alkanolamine of the general formula II

can be used as biocidal or biostatic agents in aqueous systems.

According to a preferred embodiment of the invention,1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives of thegeneral formula I in which n denotes a number in the range from 4 to 8,preferably the number 5, are used.

Alkali metal atoms can be lithium, sodium or potassium. Alkaline earthmetal atoms can be magnesium or calcium.

The alkanolamines of the general formula II contain primary, secondaryor tertiary amino and free hydroxyl groups. Both amides and esters,which are in equilibrium with one another, can be formed in the reactionof alkanolamines containing primary or secondary amino groups withcarboxylic acids, see "Surfactants in Consumer Products", editor J.Falbe, Springer-Verlag, Heidelberg 1987, page 96. For clarity, thereaction products of 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylicacids with alkanolamines to give compounds of the general formula I inwhich R¹ is the radical of an alkanolamine according to definition i)are represented here merely as amino esters. However, it is readilyclear to the expert that the 1,3,5-triazine-2,4,6-tris-alkyl-carboxylicacid derivatives thus defined also include the correspondingalkanolamides.

Typical examples of hydroxyalkyl groups having 2 to 4 carbon atoms whichcan form the group R² are 2-hydroxyethyl, 1-methyl-2-hydroxyethyl,2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 4-hydroxybutyl and2-methyl-2-hydroxypropyl groups; typical examples ofhydroxyalkyl-oxyalkylene groups having in each case 2 to 4 carbon atomsin the hydroxyalkyl and oxyalkylene radical arehydroxyethyl-oxyethylene, hydroxypropyloxyethylene,hydroxyethyl-diethyleneoxy, hydroxyethyloxypropylene andhydroxypropyl-oxypropylene groups, and typical examples ofdihydroxyalkyl groups having 3 to 6 carbon atoms are2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 1,3-dihydroxypropyl and1,3-dihydroxy-2-methyl- or -ethyl-propyl groups; and furthermore alsohydroxyethyl-, hydroxypropyl- and hydroxybutyl-oxybutylene groups.

Compounds of the general formula I in which R¹ denotes a radical of analkanolamine of the general formula II or an ammonium ion derived fromthis alkanolamine are obtainable by reaction of1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids of the generalformula

    1,3,5-triazine-2,4,6-tris -NH--(CH.sub.2).sub.n --COOH!    (III)

in which n is as defined above,

with alkanolamines of the general formula II by processes which areknown per se.

The reaction with a molar excess of the alkanolamines, based on the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids, is preferred. Theunreacted portion of the alkanolamines can be reacted with organic acidschosen from the group formed by straight-chain or branched, saturated orunsaturated fatty acids having 5 to 22 carbon atoms in order toestablish a pH of 4.5 to 9.5. Examples of the fatty acids mentioned arepentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoicacid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid,tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoicacid, octadecanoic acid, nonadecanoic acid, eicosanoic acid,heneicosanoic acid, docosanoic acid, 10-undecenoic acid, 9c-dodecenoicacid, 9c-tetradecenoic acid, 9c-hexadecenoic acid, 6c-octadecenoic acid,6t-octadecenoic acid, 9c-octadecenoic acid, 9t-octadecenoic acid,9c,12c-octadecadienoic acid, 9t,12t-octadecadienoic acid,9c,12c,15c-octadecatrienoic acid, 9c,11t,13t-octadecatrienoic acid,9c-eicosenoic acid, 5,8,11,14-eicosatetraenoic acid, 13c-docosenoicacid, 13t-docosenoic acid, 4,8,12,15,19-docosapentaenoic acid,12-hydroxy-octadenoic acid and 12-hydroxy-9c-octadecenoic acid, cindicating a cis double bond and t a trans double bond, as well astechnical grade mixtures thereof. Fatty acids and fatty acid mixtureswhich are obtainable from renewable raw materials, in particularvegetable and/or animal fats and oils, for example caproic, caprylic,capric, lauric, myristic, palmitic, stearic, oleic, ricinoleic,linoleic, erucic and behenic acid, furthermore are particularlysuitable.

Preferably, the unreacted portion of the alkanolamines is reacted withstraight-chain or branched, saturated or unsaturated fatty acids having5 to 11 carbon atoms. If no stable solutions or emulsions are obtainedin this manner, straight-chain or branched, saturated or unsaturatedfatty acids having 12 to 22 carbon atoms can additionally be used toestablish the desired hydrophilic/hydrophobic balance.

Those compounds of the general formula I which contain no secondary ortertiary amino functions are preferably employed. Secondary amines andalkanolamines can form undesirable, stable nitrosamines with nitriteions. Under certain circumstances, tertiary amines and alkanolamines canform secondary amines or alkanolamines by dealkylation. In contrast,primary amines as a rule do not form stable nitrosamines, but are usedrather as trapping agents for nitrite ions because of the rapiddissociation of the nitrosamines intermediately formed. If compounds ofthe general formula I derived from secondary alkanolamines neverthelessare to be employed, the use of a mixture of compounds derived fromprimary and secondary alkanolamines is preferred, since the formation ofthe unstable primary nitrosamines then takes place more rapidly thanthat of the secondary nitrosamines.

According to another aspect, the invention thus relates to the use ofcompounds of the general formula I which are free from secondary ortertiary amino functions and thus cannot form stable nitroso compounds,or which, if the analogous compounds of the general formula I containingsecondary or tertiary amino functions are simultaneously present,prevent the formation of stable nitroso compounds.

Biocidal and biostatic mixtures of monocarboxylic acid alkanolamides and1,3,5-triazine-2,4,6-tris-alkyl-aminocarboxylic acid alkanolamides andif appropriate alkanolammonium salts of the monocarboxylic acids and/orof the 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids can also beused.

The abovementioned biocidal and biostatic mixtures can be prepared bymixing the individual components. However, they are expediently preparedby preparing the alkanolamides or alkanolammonium salts in situ from themonocarboxylic acids and the 1,3,5-triazine-tris-alkylaminocarboxylicacids of the general formula III, in which n is as defined above, withalkanolamines of the general formula II, in which R² is as definedabove, preferably in an excess of the alkanolamines.

Primary alkanolamines or mixtures of primary and secondary alkanolaminesare preferably used.

10 to 50 mol, in particular 10 to 30 mol, of the amines of the generalformula II and 0.5 to 5 mol of the monocarboxylic acids are preferablyreacted per mole of the 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylicacids.

The reactions are carried out at a temperature in the range from 50° to180° C. Alkanolammonium salts are preferably obtained at temperatures of50° to 100° C.; alkanolamides are obtained at temperatures of >100° to180° C., in particular 130° to 180° C.

The monocarboxylic acids used are preferably straight-chain or branched,saturated or unsaturated fatty acids having 3 to 22, in particular 12 to22, carbon atoms, which are reacted with the alkanolamines in a firststage, followed by addition and reaction of the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids in a second stage.This reaction can also be carried out in another sequence or in a singlestage, although less pronounced biocidal or biostatic properties of themixture are then obtained.

Monocarboxylic acids which are furthermore used are preferablyether-carboxylic acids of the general formula

    R.sup.3 --(O--C.sub.m H.sub.2m).sub.q --O--CH.sub.2 --COOH (III)

in which

R³ denotes a straight-chain or branched alkyl or alkenyl group having 9to 18 carbon atoms,

m denotes the number 2 and/or 3 and

q denotes a number in the range from 0 to 100, preferably 0 to 20.

The reaction here can be carried out in any desired sequence, but alsoin a single stage.

Monocarboxylic acids which are likewise preferably used arearylsulphonamidocarboxylic acids of the general formula

    (R.sup.4)aryl--SO.sub.2 --N(R.sup.5)--R.sup.6 --COOH       (Va)

in which

R⁴ denotes hydrogen or a methyl or ethyl group or several groups, R⁵denotes hydrogen or a methyl, ethyl, beta-cyanoethyl or hydroxymethylgroup, R⁶ denotes an alkylene group having 4 to 6 carbon atoms and aryldenotes a phenyl, naphthyl or anthracenyl radical, and/oralkylsulphonamidocarboxylic acids of the general formula

    R.sup.7 --SO.sub.2 --NR.sup.8 --CH.sub.2 --COOH            (Vb)

in which R⁷ denotes a straight-chain or branched alkyl group having 12to 22 carbon atoms and R⁸ denotes hydrogen or the group. --CH₂ --COOH,

and/or half-esters or half-amides of the general formula Vc

    R.sup.9 --OOC--R.sup.10 --COOH                             (Vc)

in which

R⁹ is the radical of an alkanolamine of the general formula II and

R¹⁰ is an o-phenylene, vinylene or 1,2-ethylene radical. Here also, thereaction can be carried out in any desired sequence, and also in asingle stage. It has not yet been possible to determine whether thesulphonamidocarboxylic acids of the general formula Va or Vb are reactedwith the alkanolamines of the general formula II to givesulphonamidocarboxylic acid aminoalkyl esters, to givesulphonamidocarboxylic acid alkanolamides or to give mixtures thereof.For simplicity, these reaction products are always called alkanolamides.The abovementioned sulphonamidocarboxylic acids are known, for example,from DE-C 28 40 112 and DE-A 33 04 164.

Excess alkanolamine contained in the resulting reaction mixture can thenbe reacted with fatty acids having 3 to 22, preferably 3 to 11, carbonatoms, ethercarboxylic acids of the general formula IV, in which R³, mand q are as defined above, and/or aryl- or alkylsulphonamidocarboxylicacids of the general formula Va or Vb, in which R⁴, R⁵, R⁶, R⁷, R⁸ andR⁹ are as defined above, to establish a pH in the range from 4.5 to 9.5.

It is preferable to carry out all the reactions such that the reactionmixture is always kept liquid. This is achieved, for example, with thepreferred large excess of alkanolamines.

Finally, the fungicides described below can also be added to thereaction mixture after the reaction, preferably in an amount of 1 partby weight of fungicides per 10 to 100 parts by weight of the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives of thegeneral formula I, in which R¹ and n are as defined above, contained inthe biocidal or biostatic mixture.

An excess of alkanolamines present after the reaction explained above iscompletely or partly neutralized, as mentioned above, to establish asuitable pH range and with the formation of further contents ofalkanolamides or alkanolammonium salts.

Examples of straight-chain or branched, saturated or unsaturated fattyacids having 3 to 22 carbon atoms are propanoic acid, the abovementionedfatty acids having 5 to 22 carbon atoms and technical grade mixturesthereof. The reaction products of the alkanolamines with themonocarboxylic acids furthermore can serve as anti-corrosion agents inthe aqueous system.

Preferred examples of alkanolamines of the general formula II, in whichR² is as defined above, which can be used according to the invention aremono-, di- and triethanolamine, mono-, di- and tripropanolamine, mono-,di- and triisopropanolamine, 2-amino-1-butanol,2-(2'-aminoethoxy)ethanol, 2-amino-2-methyl-1-propanol and2-amino-2-ethyl-1,3-propanediol; as already mentioned, alkanolamineshaving primary amino groups or mixtures thereof with alkanolamineshaving secondary amino groups are particularly preferred.

Secondary alkanolamines which, in addition to having a singlehydroxyalkyl, hydroxyalkyl-oxyalkylene or dihydroxyalkyl group accordingto the definitions given above for R², are substituted by an alkyl grouphaving 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl,i-propyl, n-butyl, i-butyl, pentyl, cyclopentyl, hexyl or cyclohexyl,furthermore are preferred.

Such secondary monoalkanol-monoalkylamines are commercially available;typical representatives are methyl-hydroxyethyl-amine,n-butyl-hydroxyethylamine and cyclohexyl-hydroxyethyl-amine and thecorrespondingly substituted hydroxypropyl derivatives. Some of thecompounds of the general formula I derived from thesemonoalkanolmonoalkylamines have pronounced fungicidal properties whichrender the addition of other fungicides to improve the biostaticproperties superfluous.

Examples of alkylene groups having 4 to 6 carbon atoms which can formthe radical R⁶ are butylene, pentylene, hexylene, 2-methyl-propylene,2-methyl-butylene, 3-methyl-butylene, 2,2-dimethyl-propylene and2,2-dimethyl-butylene groups.

Examples of straight-chain alkyl groups having 1 to 23 carbon atomswhich can form the radical R¹ are the methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetrais decyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosyl, heneicosyl, docosyl and tricosyl group. Examples of branchedalkyl groups having 1 to 23 carbon atoms are the isopropyl, isobutyl,sec-butyl, tert-butyl, 1-methyl-butyl, 2-methyl-butyl, 3-methylbutyl(isoamyl), 1-ethyl-propyl, 1,1-dimethyl-propyl, 1,2-dimethyl-propyl and2,2-dimethyl-propyl group and the 2-branched longer-chain alkyl groups,such as the 2-methyl-pentyl, 2-ethyl-hexyl, 2-propyl-heptyl,2-butyl-octyl, 2-pentyl-nonyl, 2-hexyl-decyl, 2-heptyl-undecyl,2-octyldodecyl and 2-nonyl-tridecyl group. Examples of straight-chainalkenyl and alkynyl groups are the vinyl, allyl, 2-buten-1-yl and2-propyn-1-yl groups and the longer-chain alkenyl groups, such as the10-undecen-1-yl, 9c-octadecen-1-yl, 9t-octadecen-1-yl,9c-octadecen-12-ol-1-yl, 9c,12c-octadecadien-1-yl,9c,12c,15c-octadecatrien-1-yl, 9c-eicosen-1-yl,5,8,11,14-eicosatetraen-1-yl, 13c-docosen-1-yl and 13t-docosen-1-ylgroup, c indicating a cis double bond and t a trans double bond.Examples of branched alkenyl groups are the 3-buten-2-yl and the9c-octadecen-1-ol-12-yl group.

According to another preferred embodiment of the invention, R¹ is a2-ethyl-hexyl group.

Compounds of the general formula I in which R¹ is a straight-chain orbranched alkyl or alkenyl group having 1 to 23 carbon atoms can beprepared by esterification of the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids with thecorresponding alcohols. If the esterification is carried out with amolar excess of 2-propyn-1-ol (propargyl alcohol), based on the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids, the excesspropargyl alcohol acts as corrosion protection. The alcohols in turn areobtainable by the most diverse processes, for example the oxo process,the Ziegler process and the Guerbet process, and by hydrogenation ofnaturally occurring, animal and/or vegetable fats and oils. Examples ofthese alcohols are hexanol, heptanol, octanol, nonanol, decanol,dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, docosanol,2-methylpentanol, 2-ethyl-hexanol, 2-propyl-heptanol, 2-butyl-octanol,2-pentyl-nonanol, 2-hexyl-decanol, 2-heptyl-undecanol,2-octyl-dodecanol, 2-nonyl-tridecanol, 1,12-octadecane-diol,10-undecen-1-ol, 9c-octadecen-1-ol, 9t-octadecen-1-ol,9c-octadecene-1,12-diol, 9c,12c-octa-decadien-1-ol,9c,12c,15c-octadecatrien-1-ol, 9c-eicosen-1-ol,5,8,11,14-eicosatetraen-1-ol, 13c-docosen-1-ol and 13t-docosen-1-ol, cindicating a cis double bond and t a trans double bond, and technicalgrade mixtures thereof.

According to another preferred embodiment of the invention,1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives of thegeneral formula I in which R¹ is a straight-chain or branched alkyl oralkenyl group having 12 to 18 carbon atoms are used.

Examples of cycloalkyl groups having 5 to 6 carbon atoms in the cyclicradical which are optionally substituted by an alkyl group having 1 to 4carbon atoms or several groups are the cyclopentyl, cyclohexyl, 1-, 2-,3- and 4-methylcyclohexyl and the 3,3,5-trimethyl-cyclohexyl group, itbeing possible for the substituents to be either in the cis or in thetrans position. The compounds of the general formula I in which R¹ hasthe meaning given can be prepared by esterification of the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids with thecorresponding alcohols, for example cyclopentanol or cyclohexanol.

Examples of polyols having 2 to 15 carbon atoms and 2 to 6 hydroxylgroups are ethylene glycol, propylene glycol, glycerol, di-, tri- andtetraglycerol, di- and trimethylolpropane, pentaerythritol, di- andtripentaerythritol, arabitol, adonitol, xylitol, sorbitol, mannitol anddulcitol. Examples of addition products of ethylene oxide or propyleneoxide on one of these polyols are di-, tri- and tetraethylene glycol anddi-, tri- and tetrapropylene glycol. The polyols mentioned are reactedin a molar excess, based on the polyols, with the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids, so that as a rulean ester group is formed with only one hydroxyl group of the polyols.

According to another preferred embodiment of the invention,1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives of thegeneral formula I in which R¹ is a radical of a polyol chosen from thegroup formed by ethylene glycol, propylene glycol, glycerol,trimethylolpropane and pentaerythritol are used.

According to another preferred embodiment of the invention,1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives of thegeneral formula I in which R¹ is a radical of a polyethylene glycol orpolypropylene glycol having a molecular weight in the range from 106 to1000 are used.

R¹ can also be a radical of a mixed polyethylene/polypropylene glycolhaving the abovementioned molecular weight. The free hydroxyl group ofthe radical of a polyethylene glycol, polypropylene glycol or mixedpolyethylene/polypropylene glycol furthermore can be substituted by analkyl group having 1 to 4 carbon atoms, for example the methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl group.

Examples of straight-chain or branched, saturated or unsaturated fattyalcohols having 6 to 22 carbon atoms have already been given above. Theaddition products of ethylene oxide and/or propylene oxide on thesealcohols can also be reacted with the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids.

According to another preferred embodiment of the invention,1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives of thegeneral formula I in which R¹ is a radical of an addition product of 2to 50, in particular 2 to 20, mol of ethylene oxide and/or propyleneoxide on straight-chain or branched fatty alcohols having 12 to 18carbon atoms are used.

Phenylalkyl groups having 1 to 4 carbon atoms in the alkyl radical are,for example, the benzyl, 1-phenyl-ethyl and 2-phenyl-ethyl group.Compounds of the general formula I, in which R¹ has one of the meaningsgiven, can be prepared by reaction of the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids with thecorresponding alcohols; the benzyl group is preferred.

Typical representatives of hydroxycarboxylic acids having 2 to 18 carbonatoms are, for example, 12-hydroxy-9-octadecenoic acid (ricinoleic acid)or 12-hydroxy-octadecanoic acid (12-hydroxystearic acid), which arelikewise reacted in a molar excess with the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acids to give compoundsof the general formula I in which R¹ is a radical of a hydroxycarboxylicacid having 2 to 18 carbon atoms.

The biocidal and biostatic action of the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid-derivatives usedaccording to the invention extends to bacteria, yeasts and fungi. Thelimits between a biocidal and a biostatic action merge here. Either thebiocidal (germ-destroying) or the biostatic (growth-inhibiting) actionpredominates, depending on the amounts used and the duration of action.If a fungicide is also used in addition to the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives,synergistic effects occur, that is to say the actions are mutuallyintensified. Examples of fungicides are pyrithione and derivativesthereof, N-alkyl- or N-aryl-, in particular N-cyclohexyl-diazeniumdioxide salts, for example with potassium, aluminium, tin or copper asthe metal component (Ullmanns Encyklopadie der technischen Chemie(Ullmann's Encyclopedia of Industrial Chemistry), 4th edition, volume17, Verlag Chemie, Weinheim 1979, page 369), phenols, cresols,1,2-benzisothiazolin-3-one and derivatives thereof and 2-methyl- and2-octyl-4-isothiazolin-3-one, halogen-free compounds being preferred.Fungicides which are water-soluble and stable to alkali furthermore arepreferably employed.

According to another preferred embodiment of the invention, pyrithioneor derivatives thereof and/or N-alkyl- or N-aryl-, in particularN-cyclohexyl-diazenium dioxide salts, for example with potassium,aluminium, tin or copper as the metal component, are used as thefungicides. Pyrithione is the abbreviated name for 2-pyridine-thiol1-oxide, which is in tautomeric equilibrium with1-hydroxy-2-pyridinethione. Possible derivatives of pyrithione are theammonium, sodium, magnesium and zinc salts and 2,2'-dithiobis(pyridine1,1'-dioxide), the disulphide of pyrithione. Under certaincircumstances, the anion of pyrithione can be precipitated with heavymetals. In contrast, the abovementioned N-alkyl- and N-aryl-diazeniumdioxide salts also have complexing properties, in addition to fungicidalproperties. A mixture of pyrithione or derivatives thereof and theabovementioned N-alkyldiazenium dioxide salts is therefore preferablyused. However, it is also possible to employ only pyrithione orderivatives thereof, the fungicidal action being retained in the absenceof significant amounts of heavy metals. Since combinations of thefungicides mentioned with the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivativesaccording to the invention show synergistic effects, very small amountsthereof are adequate for the use according to the invention in aqueoussystems.

According to another preferred embodiment of the invention, the aqueoussystems contain 0.05 to 0.40% by weight of the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives and0.0001 to 0.2% by weight, preferably 0.001 to 0.1, in particular 0.001to 0.02% by weight, of fungicides, based on the total formulation.

Uses in virtually any desired aqueous or water-containing systems arepossible, for example in metal-working liquids, coolants for coolingcirculations, cleaning agents, hydraulic fluids, cosmetics and paints.For use in cosmetics, these are preferably adjusted to a pH in the rangefrom 4.5 to 7.0 by the process described above. In contrast, coolinglubricants are preferably adjusted to a pH in the range from 7.5 to 9.5.

According to another preferred embodiment of the invention, the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives are usedin cooling lubricants.

Cooling lubricants are aqueous liquids which are used for cooling andlubrication, for example, during drilling, grinding, milling, turning,cutting, sawing, abrading or thread cutting or during rolling or drawingof metals. These can be classified into three groups, according to themineral oil content:

a) synthetic cooling lubricants which are free from mineral oil,

b) semi-synthetic cooling lubricants which comprise about 10 to 60% byweight of mineral oil and

c) cooling lubricants which comprise about 60 to 80% of mineral oil.

The cooling lubricants furthermore can comprise polyglycols. Instead ofmineral oils, it is also possible to use naturally occurring orsynthetic fatty acid esters, for example rape oil or ester oils.

Further additives, such as corrosion inhibitors, copper passivators,antiwear agents, emulsifiers, carriers, precipitating agents,oxygen-trapping agents, complexing agents or foam prevention agents, canbe added to all three types of cooling lubricants.

Examples of corrosion inhibitors are organic acids and salts and estersthereof, for example benzoic acid, p-tert-butylbenzoic acid, disodiumsebacate, triethanolamine laurate, isononanoic acid, the triethanolaminesalt of p-toluenesulphonamidocaproic acid, sodium N-lauroylsarcosinateor nonylphenoxyacetic acid, or polycarboxylic acids; nitrogen-containingsubstances, for example fatty acid alkanolamides, imidazolines,oxazolines, triazoles, triethanolamine, fatty amines andN-acylsarcosines, or inorganic nitrites or nitrates;phosphorus-containing substances, for example amine phosphates,phosphonic acids, phosphonates, phosphonocarboxylic acids andphosphinocarboxylic acids, or inorganic phosphates, such as NaH₂ PO₄,and sulphur-containing substances, for example salts ofpetroleum-sulphonates or alkylbenzenesulphonates, or heterocycliccompounds which contain one sulphur atom or more in the ring.

Copper passivators which can be used are, for example, benzotriazoles,methylene-bis-benzotriazoles, such as sodium 2-mercaptobenzotriazole,thiadiazoles, for example 2,5-dimercapto-1,3,4-thiadiazole derivatives,or tolyltriazoles.

Antiwear agents can be AW (antiwear) or EP (extreme pressure) additives,for example substances containing sulphur, phosphorus or halogen, suchas sulphonated fats and olefins, tritolyl phosphate, mono- and diestersof phosphoric acid, addition products of ethylene oxide and/or propyleneoxide on polyhydroxy compounds, which are optionally partly esterifiedwith fatty acids, chloroparaffins or ethoxylated phosphate esters,chlorine-free compounds being preferred.

Examples of emulsifiers are ether-carboxylic acids, fatty acidalkanolamides, sodium petroleum sulphonates, mono- or diesters or-ethers of polyethylene glycols, polypropylene glycols or mixedpolyethylene/polypropylene glycols or fatty acid soaps.

Carriers which can be used are, for example, poly(meth)acrylic acid andits salts, hydrolysed polyacrylonitrile, polyacrylamide and copolymersthereof, ligninsulphonic acid and salts thereof, starch and starchderivatives, cellulose, alkylphosphonic acids,1-amino-alkyl-1,1-diphosphonic acids and their salts, polymaleic acidsand other polycarboxylic acids, ester oils, naturally occurring orsynthetic fatty acid esters, for example rape oil, or alkali metalphosphates.

Examples of precipitating agents are alkali metal phosphates or alkalimetal carbonates.

Examples of oxygen-trapping agents are alkali metal sulphates,morpholine and hydrazine.

The 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivativesaccording to the invention themselves have complexing properties.However, it is also possible to add other complexing agents, for examplephosphonic acid derivatives, nitrilotriacetic acid orethylenediamine-tetraacetic acid and salts thereof. Furthermore, theN-alkyl- or N-aryldiazenium dioxide salts optionally to be employed asfungicides also have complexing properties, to which reference hasalready been made.

Examples of foam prevention agents are distearylsebacic acid diamide,distearyladipic acid diamide or ethylene oxide addition products and/orpropylene oxide addition products of such amides, fatty alcohols andethylene oxide addition products and/or propylene oxide additionproducts thereof, naturally occurring and synthetic waxes, siliconecompounds, silicic acid derivatives and pyrogenic silicon dioxide.

The invention accordingly furthermore relates to cooling lubricantswhich comprise

a) 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives ofthe above general formula I, in which R¹ and n are as defined above,

b) fungicides,

c) water,

d) if appropriate mineral oil,

e) if appropriate emulsifiers and/or other auxiliaries,

f) if appropriate corrosion inhibitors,

the lubricants comprising the1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivatives in anamount of 0.05 to 0.40% by weight and the fungicides in an amount of0.0001 to 0.2% by weight, preferably 0.001 to 0.1, in particular 0.001to 0.02% by weight, based on the total amount of cooling lubricant.

Particularly preferred cooling lubricants are those which comprise, asemulsifiers and/or other auxiliaries

a) ether-carboxylic acids of the general formula IV, in which R³, m andq are as defined above, in the form of their alkanolamides and/oralkanolammonium salts with alkanolamines of the general formula II, inwhich R² is as defined above,

b) fatty acid alkanolamides based on straight-chain or branched,saturated or unsaturated fatty acids having 12 to 22 carbon atoms andamines of the general formula II,

c) aryl- and alkylsulphonamidocarboxylic acids of the general formula Vaor Vb, in which R⁴, R⁵, R⁶, R⁷ and R⁸ are as defined above, in the formof their alkanolamides and/or alkanolammonium salts with alkanolaminesof the general formula II, in which R² is as defined above,

d) straight-chain or branched, unsaturated or saturated carboxylic acidshaving 5 to 22, preferably 5 to 11, carbon atoms to establish a pH inthe range from 7.5 to 9.5, or

e) straight-chain or branched fatty alcohols having 12 to 18 carbonatoms.

Other particularly preferred cooling lubricants comprising pyrithione orderivatives thereof and/or N-alkyldiazenium dioxide salts as fungicides.

The cooling lubricants of the invention can be prepared by mixing theindividual components together. If the cooling lubricants of theinvention are to have a content of fatty acid alkanolamides, it ispreferable for the compounds of the general formula I to be prepared inthe manner described above in the form of their mixtures with the fattyacid alkanolamides. This process furthermore offers the advantage thatexclusively liquid reaction mixtures are obtained, which can be furtherprocessed without extra measures, for example comminution or dissolvingin suitable solvents.

The invention is described in more detail below with the aid ofparticularly preferred embodiment examples.

Examples 1 to 25 show the preparation of derivatives, used according tothe invention, of 2,4,6-tris-(omega'-carboxypentylamino)-1,3,5-triazine,called triazinecarboxylic acid for short below, which is commerciallyobtainable or can be obtained by reaction of cyanuric chloride with thesodium salt of 6-aminohexanoic acid in accordance with EP-B 0 046 139.

The triazinecarboxylic acid can be used as the commercially availableproduct or in the form of the commercially available aqueous product. Asolid product containing about 50% by weight of water was employed inthe following examples.

EXAMPLE 1

75 g (0.714 mol; 26.7 mol per mole of triazinecarboxylic acid) ofdiethanolamine were heated to 60° C. and 25 g (0.0267 mol) oftriazinecarboxylic acid were added, while stirring, until a clearsolution was formed.

100 g of a clear, low-viscosity liquid were obtained.

EXAMPLE 2

75 g (0.714 mol) of diethanolamine were stirred with 25 g (0.0267 mol)of triazinecarboxylic acid. After a reaction time of several hours at150° to 160° C., 10 g of water were distilled off.

The final acid number was 10 mg of KOH/g.

90 g of a clear, medium-viscosity liquid were obtained.

EXAMPLE 3

75 g (1.230 mol; 46.1 mol per mole of triazinecarboxylic acid) ofmonoethanolamine were heated to 60° C. and 25 g (0.0267 mol) oftriazinecarboxylic acid were added, while stirring, until a clearsolution was formed.

100 g of a clear, low-viscosity liquid were obtained.

EXAMPLE 4

75 g (1.230 mol) of monoethanolamine were stirred with 25 g (0.0267 mol)of triazinecarboxylic acid at 60° C. and the mixture was heated to 140°to 143° C. After a reaction time of 10 hours, 18 g of water weredistilled off.

The final acid number was 12 mg of KOH/g.

A white, solid product was obtained.

EXAMPLE 5

75 g (0.843 mol; 31.5 mol per mole of triazinecarboxylic acid) of2-amino-1-butanol were heated to 60° C. and 25 g (0.0267 mol) oftriazinecarboxylic acid were added, while stirring, until a clearsolution was formed.

100 g of a clear, low-viscosity liquid were obtained.

EXAMPLE 6

863 g (9.697 mol; 31.5 mol per mole of triazinecarboxylic acid) of2-amino-1-butanol were stirred with 287 g (0.307 mol) oftriazinecarboxylic acid at 60° C. and the mixture was heated to 145° C.After a reaction time of 20 hours, 150 g of water were distilled off.

The final acid number was 10 mg of KOH/g.

1000 g of a clear, low-viscosity liquid were obtained.

EXAMPLE 7

75 g (0.714 mol; 26.7 mol per mole of triazinecarboxylic acid) of2-(2'-aminoethoxy)ethanol were stirred with 25 g (0.0267 mol) oftriazinecarboxylic acid at 60° C. until a clear solution was formed.

100 g of a clear, low-viscosity liquid were obtained.

EXAMPLE 8

375 g (3.571 mol; 26.7 mol per mole of triazinecarboxylic acid) of2-(2'-aminoethoxy)ethanol were stirred with 125 g (0.134 mol) oftriazinecarboxylic acid at 60° C. and the mixture was heated to 145° C.After a reaction time of 16 hours, 73 g of water were distilled off.

The final acid number was 7 mg of KOH/g.

427 g of a white, pasty product were obtained.

EXAMPLE 9

20 g (0.190 mol; 7.1 mol per mole of triazinecarboxylic acid) of2-(2'-aminoethoxy)ethanol and 55 g (0.618 mol; 23.1 mol per mole oftriazinecarboxylic acid) of 2-amino-1-butanol were heated to 60° C. andstirred with 25 g (0.0267 mol) of triazinecarboxylic acid until a clearsolution was formed.

100 g of a clear, low-viscosity liquid were obtained.

EXAMPLE 10

228 g (2.171 mol; 7.1 mol per mole of triazinecarboxylic acid) of2-(2'-aminoethoxy)ethanol and 627 g (7.045 mol; 23.1 mol per mole oftriazinecarboxylic acid) of 2-amino-1-butanol were stirred with 285 g(0.304 mol) of triazinecarboxylic acid at 60° C. and the mixture washeated to 145° C. After a reaction time of 16 hours, 140 g of water weredistilled off.

The final acid number was 13 mg of KOH/g.

1000 g of clear, medium-viscosity liquid were obtained.

EXAMPLE 11

75 g (0.758 mol; 28.4 mol per mole of triazinecarboxylic acid) of AMP 90(2-amino-2-methyl-1-propanol with 10% of water) were heated to 60° C.and stirred with 25 g (0.0267 mol) of triazinecarboxylic acid until aclear solution was formed.

A clear, low-viscosity liquid was obtained.

EXAMPLE 12

833 g (8.424 mol; 31.5 mol per mole of triazinecarboxylic acid) of AMP90 were heated to 60° C. and stirred with 250 g (0.267 mol) oftriazinecarboxylic acid and the mixture was heated to 140° to 145° C.After a reaction time of 20 hours, 240 g of water were distilled off.

The final acid number was 15 mg of KOH/g.

843 g of an almost clear, high-viscosity product were obtained.

EXAMPLE 13

75 g (0.630 mol; 23.6 mol per mole of triazinecarboxylic acid) of AEPD(2-amino-2-ethyl-1,3-propanediol) were heated to 60° C. and stirred with25 g (0.0267 mol) of triazinecarboxylic acid until a clear solution wasformed.

100 g of a clear, medium-viscosity liquid were obtained.

EXAMPLE 14

990 g (8.319 mol; 23.6 mol per mole of triazinecarboxylic acid) of AEPDwere heated to 60° C. and stirred with 330 g (0.353 mol) oftriazinecarboxylic acid, and the mixture was heated to 140° to 145° C.After a reaction time of 16 hours, 320 g of water were distilled off.

The final acid number was 10 mg of KOH/g.

1000 g of a clear, high-viscosity liquid were obtained.

EXAMPLE 15

75 g (1.000 mol; 37.4 mol per mole of triazinecarboxylic acid) ofmonoisopropanolamine were heated to 60° C. and stirred with 25 g (0.0267mol) of triazinecarboxylic acid until a clear solution was formed.

100 g of a low-viscosity liquid were obtained.

EXAMPLE 16

375 g (5.000 mol; 37.4 mol per mole of triazinecarboxylic acid) ofmonoisopropanolamine were heated to 60° C. and stirred with 125 g (0.134mol) of triazinecarboxylic acid, and the mixture was heated to 140° C.After a reaction time of 16 hours, 74 g of water were distilled off.

The final acid number was 12 mg of KOH/g.

426 g of a clear, low-viscosity liquid were obtained.

EXAMPLE 17

75 g (0.503 mol; 18.9 mol per mole of triazinecarboxylic acid) oftriethanolamine were heated to 60° C. and stirred with 25 g (0.0267 mol)of triazinecarboxylic acid until a clear solution was formed.

100 g of a clear, low-viscosity liquid were obtained.

EXAMPLE 18

750 g (5.034 mol; 18.9 mol per mole of triazinecarboxylic acid) oftriethanolamine were heated to 60° C. and stirred with 250 g (0.267 mol)of triazinecarboxylic acid, and the mixture was heated to 140° to 145°C. After a reaction time of 16 hours, 130 g of water were distilled off.

The final acid number was 6 mg of KOH/g.

870 g of a clear, medium-viscosity liquid were obtained.

EXAMPLE 19

8 parts of triazinecarboxylic acid and 1 part of2-(8-heptadecenyl)-4,5-dihydro-1-(2-hydroxyethyl)imidazole were added to6 parts by weight of monoisopropanolamine at ambient temperature, whilestirring. The mixture was stirred until a clear, amber-coloured liquidhad formed.

EXAMPLE 20 1st Stage

130 g (1.238 mol; 4.8 mol per mole of triazinecarboxylic acid) of2-(2'-aminoethoxy)ethanol and 370 g (4.157 mol; 16.2 mol per mole oftriazinecarboxylic acid) of 2-amino-1-butanol were reacted with 190 g(0.674 mol; 2.6 mol per mole of triazinecarboxylic acid) of olein at145° C. After a reaction time of 10 hours, 12 g of water were distilledoff.

678 g of a liquid product having an acid number of 7 mg of KOH/g wereobtained.

2nd Stage

678 g of the product of stage 1 were heated to 70° C. and stirred with240 g (0.256 mol) of triazinecarboxylic acid.

A clear, viscous liquid was obtained.

EXAMPLE 20a 1st Stage

130 g (1.238 mol) of 2-(2'-aminoethoxy)ethanol and 370 g (4.157 mol) of2-amino-1-butanol were reacted with 190 g (0.674 mol) of olein at 145°C. After a reaction time of 10 hours, 12 g of water were distilled off.

678 g of a liquid product having an acid number of 7 mg of KOH/g wereobtained.

2nd Stage

678 g of the product of stage 1 were heated to 70° C. and stirred with240 g (0.256 mol) of triazinecarboxylic acid and 174 g (0.497 mol; 1.9mol per mole of triazinecarboxylic acid) of a commercially availablearylsulphonamidocarboxylic acid having a molecular weight of about 350(HostacorR H liquid), called sulphonamidocarboxylic acid for shortbelow.

A stable, slightly cloudy liquid was obtained.

EXAMPLE 20b 1st Stage

130 g (1.238 mol) of 2-(2'-aminoethoxy)ethanol and 370 g (4.157 mol) of2-amino-1-butanol were reacted with 190 g (0.674 mol) of olein at 145°C. After a reaction time of 10 hours, 12 g of water were distilled off.

678 g of a liquid product having an acid number of 7 mg of KOH/g wereobtained.

2nd Stage

678 g of the product of stage 1 were heated to 70° C. and stirred with240 g (0.0256 mol) of triazinecarboxylic acid and 106 g (0.148 mol; 0.6mol per mole of triazinecarboxylic acid) of ether-carboxylic acid(commercially available reaction product of 1 mol of chloroacetic acidwith a condensation product of 1 mol of a technical grade oleyl alcoholwith 10 mol of ethylene oxide).

A clear, viscous liquid was obtained.

EXAMPLE 20c

130 g (1.238 mol) of 2-(2'-aminoethoxy)ethanol and 370 g (4.157 mol) of2-amino-1-butanol were heated to 70° C. and the mixture was stirred with174 g (0.497 mol) of sulphonamidocarboxylic acid and 240 g (0.256 mol)of triazinecarboxylic acid.

A pale, clear, medium-viscosity liquid was obtained.

EXAMPLE 20d

130 g (1.238 mol) of 2-(2'-aminoethoxy)ethanol, 370 g (4.157 mol) of2-amino-1-butanol, 174 g (0.497 mol) of sulphonamidocarboxylic acid and240 g (0.256 mol) of triazinecarboxylic acid are reacted at 145° C.After a reaction time of 12 hours, 143 g of water were distilled off.

771 g of a medium-viscosity, clear, liquid product having a final acidnumber of 25 mg of KOH/g were obtained.

EXAMPLE 20e

130 g (1.238 mol) of 2-(2'-aminoethoxy)ethanol and 370 g (4.157 mol) of2-amino-1-butanol were heated to 70° C. and stirred with 106 g (0.148mol) of ether-carboxylic acid and 240 g (0.256 mol) oftriazinecarboxylic acid.

A pale, medium-viscosity liquid was obtained.

EXAMPLE 20f

130 g (1.238 mol) of 2-(2'-aminoethoxy)ethanol, 370 g (4.157 mol) of2-amino-1-butanol, 106 g (0.148 mol) of ether-carboxylic acid and 240 g(0.256 mol) of triazinecarboxylic acid were reacted at 145° C. After areaction time of 13 hours, 137 g of water were distilled off.

709 g of a clear, medium-viscosity product having a final acid number of20 mg of KOH/g were obtained.

EXAMPLE 21

678 g of the liquid from the first stage of Example 20 were heated to60° C. and stirred with 240 g (0.256 mol) of triazinecarboxylic acid andthe mixture was heated to 140° to 150° C. After a reaction time of 10hours, 138 g of water were distilled off.

The final acid number was 14 mg of KOH/g.

780 g of a clear, medium-viscosity product were obtained.

EXAMPLE 22

273 g (1.019 mol; 2.8 mol per mole of triazinecarboxylic acid) of acommercially available technical grade oleyl alcohol (about 90%strength, iodine number about 95) were heated to 80° to 100° C. andstirred slowly with 333 g (0.356 mol) of triazinecarboxylic acid, andthe mixture was heated to a maximum of 200° C. After a reaction time ofabout 20 hours, 206 ml of water were distilled off.

The final acid number was 18 mg of KOH/g.

A clear, medium-viscosity liquid was obtained.

EXAMPLE 23

350 g (2.692 mol; 15 mol per mole of triazinecarboxylic acid) of2-ethylhexanol were heated to 100° C. and stirred with 168 g (0.179 mol)of triazinecarboxylic acid and the mixture was heated slowly to amaximum of 190° C. After a reaction time of 10 hours, 358 g of water andethylhexanol were distilled off.

The final acid number was 15 mg of KOH/g.

160 g of a clear, viscous liquid were obtained.

EXAMPLE 24

273 g (3.592 mol; 10.1 mol per mole of triazinecarboxylic acid) of1,2-propylene glycol were heated to 100° C. and stirred with 333 g(0.356 mol) of triazinecarboxylic acid, and the mixture was heated to amaximum of 168° C. After a reaction time of 7 hours, 276 ml of waterwere distilled off.

The final acid number was 38 mg of KOH/g.

330 g of a viscous, pale liquid were obtained.

EXAMPLE 25

324 g (3.000 mol; 8.4 mol per mole of triazinecarboxylic acid) of benzylalcohol were stirred with 333 mg (0.356 mol) of triazinecarboxylic acidand the mixture was heated under nitrogen to a maximum of 180° C. Aftera reaction time of 9 hours, 180 ml of water were distilled off.

The final acid number was 21 mg of KOH/g.

477 g of a low-viscosity liquid were obtained.

EXAMPLE 26

375 g (3.2 mol; 23.97 mol per mole of triazinecarboxylic acid) ofN-butylethanolamine were reacted with 125 g (0.13 mol) oftriazinecarboxylic acid at 145° C. After a reaction time of 14 hours, 85g of water were distilled off.

415 g of a liquid product having an acid number of 13 mg of KOH/g wereobtained.

EXAMPLE 27

167 g (1.43 mol; 8 mol per mole of triazinecarboxylic acid) ofN-butylethanolamine were reacted with 167 g (0.18 mol) oftriazinecarboxylic acid at 148° C. After a reaction time of 14 hours, 56g of water were distilled off.

278 g of a viscous product with an acid number of 7 mg of KOH/g wereobtained.

EXAMPLE 28

100 g (0.85 mol; 2 mol per mole of triazinecarboxylic acid) ofN-butylethanolamine and 100 g (0.95 mol; 2.22 mol per mole oftriazinecarboxylic acid) of 2-(2'-aminoethoxy)ethanol and 100 g (1.33mol; 3.11 mol per mole of triazinecarboxylic acid) ofmonoisopropanolamine were reacted with 200 g (0.21 mol) oftriazinecarboxylic acid at 150° C. After a reaction time of 10 hours, 65g of water were distilled off.

435 g of a medium-viscosity product having an 20 acid number of 14 mg ofKOH/g were obtained.

EXAMPLE 29

516 g (4.9 mol; 8.75 mol per mole of triazinecarboxylic acid) of2-(2'-aminoethoxy)ethanol and 248 g (3.3 mol; 5.89 mol per mole oftriazinecarboxylic acid) of monoisopropanolamine were reacted with 526 g(0.56 mol) of triazinecarboxylic acid at 150° C. After a reaction timeof 14 hours, 290 g of water were distilled off.

1000 g of a liquid product having an acid number of 11 mg of KOH/g wereobtained.

EXAMPLE 30 1st Stage

117 g (1 mol) of N-butylethanolamine were heated to 110° C. and 148 g (1mol) of phthalic anhydride were slowly added, while cooling. Thereaction time lasted 4 hours at a maximum of 130° C.

265 g of a solid, vitreous product with an acid number of 211 mg ofKOH/g were obtained.

2nd Stage

50 g of stage 1 were mixed with 50 g of product from Example 10 at 100°C.

A viscous product having an acid number of 115 mg of KOH/g was obtained.

EXAMPLE 31

50 g of Korantin PA (phthalic acid 2-methyl-2-ethylhexylamide) weremixed with 50 g of product from Example 10 at 50° C.

A viscous product having an acid number of 88 mg of KOH/g was obtained.

Comparison Examples 1 to 3 and Examples 32 to 54

A number of the 1,3,5-triazine-2,4,6-tris-alkyl-aminocarboxylic acidderivatives thus prepared were formulated with water, spindle oil andother additives stated in each case, and in some examples withfungicides, to give mixtures which result in cooling lubricants in adilution with water of 1:20 to 1:80.

Furthermore, mixtures without biocides were formulated in ComparisonExamples 1 and 2 and a mixture with a boric acid alkanolaminecondensation product as the biocidal agent was formulated in ComparisonExample 3.

Data in % below always relate to parts by weight.

The information in the "Exp." column relates to the explanations ofTable 1. All the chemicals listed in Table 1 are commerciallyobtainable.

Table 1: EXPLANATIONS

1 Tall oil distillate with 25-30% resin (acid number 155-190)

2a) isononanoic acid

b) 2,2-dimethyl-octanoic acid

3 Spindle oil, viscosity: 22 m² /s at 40° C.

4a) reaction product of 1 mol of chloroacetic acid with a condensationproduct of 1 mol of a technical grade oleyl alcohol with 10 mol ofethylene oxide (ether-carboxylic acid)

b) reaction product of 1 mol of chloroacetic acid with a condensationproduct of 1 mol of C₉ - to C₁₃ -oxo-alcohols with 3 mol of ethyleneoxide and 2 mol of propylene oxide (ether-carboxylic acid)

5a) technical grade oleyl alcohol (about 90% strength, iodine numberabout 95)

b) 2-hexyl-decanol

6a) condensation product of 1 mol of a technical grade mixture of oleyland cetyl alcohol with 5 mol of ethylene oxide

b) fatty alcohol polyglycol ether (EmulsogenR LP)

7a) condensation product of 40 parts by weight of diethanolamine with 60parts by weight of olein

b) as a) with addition of 20% of ethanolamine, based on the total amountof condensation product and ethanolamine

8a) diethylene glycol

b) butyldiglycol

c) butylglycol

9a) sodium petroleumsulphonate having a molecular weight of about 460

b) sodium alkylbenzenesulphonate having a molecular weight of about 350

10 50% strength potassium hydroxide solution

11 fungicidal mixture of 10% of the sodium salt of pyrithione 10% ofN-(cyclohexyl-diazenium dioxide) potassium hydrate in the form of a 30%strength aqueous solution 10% of propylene glycol 70% of demineralizedwater

12 condensation product of 1 mol of boric acid with 3 mol ofethanolamine

13 arylsulphonamidocarboxylic acid having a molecular weight of about350 (HostacorR H liquid; acid content about 90%, remainder solubilizingagent)

    ______________________________________                                                                 Exp.                                                 ______________________________________                                        Comparison Example 1                                                          7% of fatty acids        1                                                    2% of sulphonates        9b)                                                  5% of fatty acid alkanolamides                                                                         7b)                                                  2% of auxiliaries        8a)                                                  1% of auxiliaries        10                                                   83% of spindle oil       3                                                    Comparison Example 2                                                          8% of fatty acids        1                                                    17% of sulphonates       9a)                                                  4% of fatty acid alkanolamides                                                                         7a)                                                  3% of auxiliaries        8c)                                                  2% of auxiliaries        10                                                   36% of spindle oil       3                                                    30% of water                                                                  Comparison Example 3                                                          20% of boric acid product                                                                              12                                                   10% of fatty acids       1                                                    10% of fatty acid alkanolamides                                                                        7a)                                                  10% of auxiliaries       8b)                                                  20% of spindle oil       3                                                    30% of water                                                                  Example 32                                                                    25% of Example 1                                                              31% of spindle oil       3                                                    10% of fatty acids       1                                                    5% of fatty acids        2b)                                                  4% of ether-carboxylic acids                                                                           4b)                                                  6% of fatty alcohols     5a)                                                  5% of nonionic emulsifiers                                                                             6a)                                                  1% of fungicides         11                                                   13% of water                                                                  Example 33                                                                    25% of Example 2                                                              31% of spindle oil       3                                                    10% of fatty acids       1                                                    5% of fatty acids        2b)                                                  4% of ether-carboxylic acids                                                                           4b)                                                  6% of fatty alcohols     5a)                                                  14% of water                                                                  5% of nonionic emulsifiers                                                                             6a)                                                  Examples 34                                                                   25% of Example 4                                                              31% of spindle oil       3                                                    10% of fatty acids       1                                                    5% of fatty acids        2b)                                                  4% of ether-carboxylic acids                                                                           4b)                                                  6% of fatty alcohols     5a)                                                  5% of nonionic emulsifiers                                                                             6a)                                                  14% of water                                                                  Example 35                                                                    22% of Example 6                                                              11% of fatty acids       2a)                                                  17% of fatty acids       1                                                    6% of ether-carboxylic acids                                                                           4a)                                                  9% of fatty acid alkanolamides                                                                         7a)                                                  4% of fatty alcohols     5a)                                                  22% of spindle oil       3                                                    8% of water                                                                   1% of fungicides         11                                                   Example 36                                                                    21% of Example 10                                                             21% of fatty acids       1                                                    11% of fatty acids       2a)                                                  7% of ether-carboxylic acids                                                                           4a)                                                  5% of fatty alcohols     5b)                                                  20% of spindle oil       3                                                    13% of water                                                                  2% of fungicides         11                                                   Example 37                                                                    25% of Example 14                                                             31% of spindle oil       3                                                    10% of fatty acids       1                                                    3% of fatty acids        2a)                                                  8% of fatty alcohols     5a)                                                  5% of nonionic emulsifiers                                                                             6a)                                                  4% of ether-carboxylic acids                                                                           4b)                                                  1% of fungicides         11                                                   13% of water                                                                  Example 38                                                                    25% of Example 16                                                             31% of spindle oil       3                                                    10% of fatty acids       1                                                    5% of fatty acids        2b)                                                  4% of ether-carboxylic acids                                                                           4b)                                                  6% of fatty alcohols     5a)                                                  5% of nonionic emulsifiers                                                                             6a)                                                  1% of fungicides         11                                                   13% of water                                                                  Example 39                                                                    35% of Example 17                                                             20% of spindle oil       3                                                    10% of fatty acids       1                                                    5% of fatty acids        2a)                                                  3% of ether-carboxylic acids                                                                           4b)                                                  6% of fatty alcohols     5b)                                                  5% of nonionic emulsifiers                                                                             6a)                                                  16% of water                                                                  Example 40                                                                    19% of Example 21                                                             29% of fatty acids       1                                                    29% of spindle oil       3                                                    5% of auxiliaries        8b)                                                  3% of nonionic emulsifiers                                                                             6b)                                                  1% of fungicides         11                                                   14% of water                                                                  Example 41                                                                    20% of Example 3                                                              20% of fatty acids       1                                                    16% of fatty acids       2a)                                                  7% of ether-carboxylic acids                                                                           4a)                                                  5% of fatty alcohols     5b)                                                  18% of spindle oil       3                                                    2% of fungicides         11                                                   12% of water                                                                  Example 42                                                                    21% of Example 9                                                              21% of fatty acids       1                                                    11% of fatty acids       2a)                                                  7% of ether-carboxylic acids                                                                           4a)                                                  5% of fatty alcohols     5b)                                                  20% of spindle oil       3                                                    2% of fungicides         11                                                   13% of water                                                                  Example 43                                                                    7% of Example 25                                                              93% of Comparison Example 1                                                   Example 44                                                                    7% of Example 25                                                              91% of Comparison Example 1                                                   2% of fungicides         11                                                   Example 45                                                                    4% of Example 23                                                              96% of Comparison Example 1                                                   Example 46                                                                    4% of Example 23                                                              94% of Comparison Example 1                                                   2% of fungicides         11                                                   Example 47                                                                    4% of Example 23                                                              96% of Comparison Example 2                                                   Example 48                                                                    4% of Example 23                                                              94% of comparison Example 2                                                   2% of fungicides         11                                                   Example 49                                                                    24% of Example 20a                                                            22% of fatty acids       1                                                    29% of spindle oil       3                                                    4% of auxiliaries        8b)                                                  2% of monoethanolamine                                                        4% of nonionic emulsifiers                                                                             6a)                                                  1% of fungicides         11                                                   14% of water                                                                  Example 50                                                                    25% of Example 20b                                                            23% of fatty acids       1                                                    29% of spindle oil       3                                                    3% of auxiliaries        8b)                                                  4% of nonionic emulsifiers                                                                             6a)                                                  1% of fungicides         11                                                   14% of water                                                                  1% of monoethanolamine                                                        Example 51                                                                    23% of Example 20c                                                            28% of fatty acids       1                                                    1% of fatty alcohols     5a)                                                  4% of nonionic emulsifiers                                                                             6a)                                                  4% of auxiliaries        8b)                                                  1% of fungicides         11                                                   27% of spindle oil       3                                                    12% of water                                                                  Example 52                                                                    23% of Example 20d                                                            28% of fatty acids       1                                                    25% of spindle oil       3                                                    5% of nonionic emulsifiers                                                                             6b)                                                  2% of fatty alcohols     5b)                                                  2% of auxiliaries        8b)                                                  1% of fungicides         11                                                   14% of water                                                                  Example 53                                                                    23% of Example 20e                                                            28% of fatty acids       1                                                    1% of fatty alcohols     5a)                                                  4% of nonionic emulsifiers                                                                             6a)                                                  4% of auxiliaries        8b)                                                  1% of fungicide          11                                                   27% of spindle oil       3                                                    12% of water                                                                  Example 54                                                                    23% of Example 20f                                                            28% of fatty acids       1                                                    1% of fatty alcohol      5a)                                                  4% of nonionic emulsifiers                                                                             6a)                                                  4% of auxiliaries        8b)                                                  1% of fungicides         11                                                   27% of spindle oil       3                                                    12% of water                                                                  Example 55                                                                    21% of Example 32                                                             21% of fatty acids       1                                                    20% of spindle oil       3                                                    15.5% of water                                                                1.5% of ether-carboxylic acids                                                                         4b)                                                  2% of ether-carboxylic acids                                                                           4a)                                                  2% of nonionic emulsifiers                                                                             6b)                                                  5% of fatty alcohols     5b)                                                  11% of fatty acids       2a)                                                  1% of monoethanolamine                                                        Example 55a                                                                   98% of Example 55                                                             2% of fungicides         11                                                   Example 56                                                                    10% of Example 33                                                             30% of spindle oil       3                                                    22% of water                                                                  15% of fatty acids       1                                                    5% of fatty acids        2a)                                                  5% of fatty alcohols     5b)                                                  2% of ether-carboxylic acids                                                                           4b)                                                  4% of ether-carboxylic acids                                                                           4a)                                                  3% of monoethanolamine                                                        4% of fatty acid alkanolamide                                                                          7a)                                                  Example 56a                                                                   98% of Example 56                                                             2% of fungicides         11                                                   Example 57                                                                    10% of Example 34                                                             23% of fatty acids       2a)                                                  9% of monoethanolamine                                                        2% of ether-carboxylic acids                                                                           4b)                                                  6% of fatty alkanolamide 7a)                                                  50% of water                                                                  Example 57a                                                                   98% of Example 57                                                             2% of fungicides         11                                                   Example 58                                                                    5% of Example 33                                                              5% of Example 35                                                              23% of fatty acids       2a)                                                  10% of monoethanolamine                                                       2.5% of ether-carboxylic acids                                                                         4b)                                                  6% of fatty acid alkanolamide                                                                          7a)                                                  48.5% of water                                                                Example 58a                                                                   98% of Example 58                                                             2% of fungicides         11                                                   Example 59                                                                    20% of Example 37                                                             25% of spindle oil       3                                                    17% of fatty acids       1                                                    4% of fatty alcohols     5b)                                                  4% of nonionic emulsifiers                                                                             6b)                                                  1% of monoethanolamine                                                        29% of water                                                                  Example 59a                                                                   98% of Example 60                                                             2% of fungicides         11                                                   Example 60                                                                    20% of Example 37                                                             25% of spindle oil       3                                                    17% of fatty acids       1                                                    4% of fatty alcohols     5b)                                                  4% of nonionic emulsifiers                                                                             6b)                                                  1% of monoethanolamine                                                        29% of water                                                                  Example 60a                                                                   98% of Example 60                                                             2% of fungicides         11                                                   ______________________________________                                    

Microbiological test methods

An inoculation cycle test developed in-house was carried out. For this,the following dilutions of the formulations of Comparison Examples 1 to3 and of Examples 26 to 42 were prepared with Hamburg town water: 1.25%,2.5% and 5.0% (corresponds to 1:80, 1:40 and 1:20).

The samples were inoculated several times with a concentrated mixed germflora. The germ flora contained bacteria, yeasts and fungi from runningemulsion systems of varying origin. Their total germ count was about is10⁷ germs/ml.

The amount of mixed germ flora for inoculation of the samplescorresponded to six times the amount proposed according to DAB 9 (GermanPharmacopoeia). 6 ml of germ flora were used per 100 ml of sample.

The samples were inoculated repeatedly (a maximum of 6 inoculations) bythis method (in accordance with K. H. Wallhauβer; Praxis derSterilisation-Desinfektion-Konservierung-Keimidentifizierung (Practiceof Sterilization-Disinfection-Preservation-Germldentification), 4thEdition, Georg Thieme Verlag, Stuttgart 1988), until no furtherantimicrobial action was detectable. From experience, 1 inoculationcorresponded to 3 inoculation cycles by the DAB 9/Wallhauβer method.

This method has the following advantages:

1. A mixed germ flora such as occurs in practice is employed.

2. The samples are exposed to a massive germ load several times.

3. The method is quick and therefore appropriate for industry. Incomparison with the conventional method, which often takes severalmonths, the results are available in a maximum of 8 weeks if they do nothave to be repeated.

4. Conclusions as to the service lives of the emulsions in use in thecentral systems can be drawn from the results.

The action time of the microorganisms on the samples was about 1 week.After this time, the samples were spread out onto in each case twospecial nutrient media and incubated. The colony count was thendetermined under a microscope, and the germ count per ml of sample wasdetermined therefrom. The number of inoculation cycles after which afirst attack by germs is to be observed is shown in Table 2. This is ameasure of the activity of the biocides in the particular samples. Theformulations of Examples 27, 28, 29 and 32 based on the compounds ofExamples 2, 4, 6 and 16 proved to be particularly active. Example 28even shows a fungicidal action without addition of pyrithione orderivatives thereof. When Examples 26 and 36 were compared with Examples27 and 30 respectively, it was furthermore found that, surprisingly, thealkanolamides have a better activity than the alkanolammonium saltsderived from the same alkanolamines.

                                      TABLE 2                                     __________________________________________________________________________    Microbiological results                                                              Dilution %                                                                    1.25       2.5        5                                                Example                                                                              B  Y  F  IC                                                                              B  Y  F  IC                                                                              B  Y F  IC                                       __________________________________________________________________________    Comparison                   +++                                                                              ++                                                                              0   3                                       Example 1                                                                     Comparison                   +++                                                                              ++                                                                              0   3                                       Example 2                                                                     Comparison                   0  0 +++                                                                              18                                       Example 3                                                                     32     +++                                                                              +++                                                                              0  3 +++                                                                              0  ++  6                                                                              +  0 0  12                                       33     +++                                                                              +++                                                                              0  3 +++                                                                              0  ++ 12                                                                              0  0 0  18                                       34     +++                                                                              ++ 0  9 ++ ++ 0  12                                                                              +  0 0  18                                       35     ++ ++ 0  3 ++ ++ 0  12                                                                              0  0 0  18                                       36     +++                                                                              0  0  3 +++                                                                              0  +++                                                                               9                                                                              0  0 0  18                                       37     ++ ++ 0  3 +  0  0   6                                                                              ++ + 0   9                                       38     +++                                                                              ++ 0  6 0  0  0  18                                                                              0  0 0  18                                       39     +++                                                                              +++                                                                              0  3 +++                                                                              ++ +   6                                                                              +++                                                                              + 0   9                                       40     +++                                                                              ++ 0  3 ++ ++ 0   3                                                                              +  + 0  15                                       41     +++                                                                              ++ 0  3 ++ +  0   9                                                                              ++ + 0  15                                       42     +++                                                                              ++ 0  3 +++                                                                              +  0   6                                                                              ++ 0 0  12                                       43     +++                                                                              0  0  3 ++ 0  0   3                                                                              ++ 0 0   3                                       44     +++                                                                              +++                                                                              0  3 +++                                                                              0  0   3                                                                              ++ 0 0   3                                       45     +++                                                                              +++                                                                              0  3 +++                                                                              +++                                                                              0   3                                                                              +++                                                                              ++                                                                              0   3                                       46     +++                                                                              +++                                                                              0  3 ++ ++ 0   3                                                                              ++ ++                                                                              0   3                                       47     +++                                                                              +++                                                                              0  3 +++                                                                              +++                                                                              0   3                                                                              +++                                                                              ++                                                                              0   3                                       48     +++                                                                              ++ 0  3 ++ ++ 0   3                                                                              ++ ++                                                                              0   3                                       55     ++ ++ +  3 0  0  0  12                                                                              0  0 0  18                                       55a    ++ ++ 0  3 0  0  0  12                                                                              0  0 0  18                                       56     ++ ++ +++                                                                              3 +  +  +   6                                                                              +  + +   9                                       56a    ++ ++ 0  3 +  +  0   6                                                                              +  + 0   9                                       57     ++ ++ ++ 3 0  0  +   6                                                                              0  0 +  18                                       57a    ++ ++ 0  6 +  +  0  12                                                                              0  0 0  18                                       58     0  0  +  3 0  0  +  12                                                                              0  0 +  18                                       58a    +  +  0  6 +  +  0  12                                                                              0  0 0  18                                       59     +++                                                                              0  0  3 +++                                                                              0  +++                                                                               9                                                                              0  0 0  18                                       59a    +++                                                                              0  0  3 +++                                                                              0  0   9                                                                              0  0 0  18                                       60     +++                                                                              0  0  3 ++ 0  0   9                                                                              0  0 0  18                                       60a    +++                                                                              0  0  3 ++ 0  0   9                                                                              0  0 0  18                                       __________________________________________________________________________     +++ = severe attack  germ count/ml > 10.sup.4                                 ++ = moderate attack  germ count/ml 10.sup.3 -10.sup.4                        + = slight attack  germ count/ml < 10.sup.3                                   0 = no attack                                                                 B = bacteria                                                                  Y = yeasts                                                                    F = fungi                                                                     IC = first germ attack after x inoculation cycles                        

We claim:
 1. A method comprising using1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid amino esters andamides of the general formula ##STR2## or ##STR3## in which n denotes anumber in the range from 4 to 11,C--X is a radical of an alkanolamine ofthe general formula

    (R.sup.1).sub.3 N                                          (II)

wherein a carbon atom of the alkanolamine radical of formula 11 isdirectly bonded to an oxygen atom of the triazine as shown in formula(I), and N--Z is a radical of an alkanolamine of the general formula

    (R.sup.1).sub.2 N                                          (II')

wherein the nitrogen atom of the alkanolamine radical of formula II' isdirectly bonded to an oxygen atom of the triazine as shown in formula(I'), in which at least one of the groups R¹ is a) a hydroxyalkyl grouphaving 2 to 4 carbon atoms, b) a hydroxyalkyl-oxyalkylene group having 2to 4 carbon atoms in each of the hydroxyalkyl and oxyalkyl radicals orc) a dihydroxyalkyl group having 3 to 6 carbon atoms, and(i) in the caseof the general formula (II), if less than three of the R¹ groups havethe above meaning, the other R¹ groups are hydrogen, or if one of the R¹groups has the above meaning, a second R¹ group is an alkyl group having1 to 6 carbon atoms and a third R¹ group is hydrogen and, (ii) in thecase of general formula (II'), if only one of the R¹ groups have theabove meaning, the other R¹ group is hydrogen, as biocidal and biostaticagents in aqueous systems.
 2. The method according to claim 1 wherein nis
 5. 3. The method according to claim 1 wherein the amines of thegeneral formula (II) and (II') are primary alkanolamines or mixtures ofprimary and secondary alkanolamines having 2 to 4 carbon atoms in thehydroxyalkyl group.
 4. The method according to claim 1 furthercomprising the step of adding to said aqueous system a water-solublefungicide which is stable to alkali.
 5. The method according to claim 4wherein said fungicide is pyrithione, a pyrithione derivative,N-alkyl-diazenium dioxide salts or a mixture thereof.
 6. The methodaccording to claim 1 wherein said aqueous systems are coolinglubricants.
 7. The method according to claim 1 wherein said aqueoussystem, based on the total formulation, contains 0.05 to 0.40% by weightof the 1,3,5-triazine-2,4,6-tris-alkylaminocarboxylic acid derivativesof the general formulas (I) or (I') and 0.0001 to 0.2% by weight offungicides.